At present, the main route to the allylamines is probably the reaction of an allyl halide with ammonia. This reaction can take place both in the vapor and the liquid phases as represented by U.S. Pat. Nos. 2,216,548 and 3,175,009. The mix of mono-, di-, and triallylamines is hard to control when using an allyl halide with tertiary and even quaternary amines being the main products. Moreover, the product is an amine hydrohalide which must be neutralized with base to recover the free amine. This recovery scheme produces a corrosive by-product stream of a halide salt for disposal.
It is also known to convert the triallylamine by-product resulting from the allyl halide-ammonia reaction into diallylamine. U.S. Pat. No. 3,428,685 discloses the pyrolysis of triallylamine hydrochloride, resulting in a mixture of diallylamine and allyl chloride. U.S. Pat. No. 3,110,731 discloses a catalytic process for converting triallylamine to diallylamine in the presence of a hydrogenation catalyst such as palladium.
The allylation of nitrogen compounds containing an active hydrogen using allyl ethers and esters is known to be catalyzed by palladium complexes. U.S. Pat. No. 3,493,617 discloses the production of N-allylic substituted secondary or tertiary organic amines by reacting an allylic aryl ether or an allylic carboxylate ester of an organic carboxylic acid with an organic amine in the presence of certain metal compounds containing organic complexing ligands, the metal being palladium, platinum or rhodium and the ligands being phosphines. U.S. Pat. No. 4,083,874 discloses a process for the production of allylic amines which comprises reacting a pi-allyl palladium complex with ammonia or an amine having a reactive hydrogen attached to the nitrogen atom and a cupric salt, the palladium being stabilized by a ligand material having the formula R.sub.3 M, wherein M is phosphorus, arsenic, antimony or bismuth and R is a hydrocarbyl or hydrocarbyloxy group. It is also known that a complex of palladium and triphenyl phosphine or tributyl phosphine can be used for the disproportionation of diallylamines to the corresponding mono- and triallylamines. See U.S. Pat. No. 3,865,877.
Research Disclosure, 16906, p. 35, May 1978 discloses that allyl compounds such as allyl acetate, allyl chloride, allyl cyanide, allyl ether and allyl alcohol can be converted to allylamines by reacting the allyl compounds with a dialkylamine or ammonium salt of a carboxylic acid. Catalysts suitable for these reactions are those comprising a zero valent complex of metals such as palladium, platinum, ruthenium, nickel and cobalt bearing phosphorus organo containing ligands.
However, reacting allyl alcohol in the presence of an alumina and copper catalyst yields primarily beta-picoline. See U.S. Pat. Nos. 2,603,645 and 2,605,264.